Catalysts



patente cl Nov. 3,. 19 31 UNITED STATES T RE-MAIN, GERMANY 11o Drawing.Application filed June .25, 192?, Serial No. 201,557, and m- GermanyNovember 2?, 1926..

The present invention relates to new catalysts and to a process ofpreparing the same; more particularly it relates to catalysts comprisinga metal of the group including nickel,

t5 cobalt, and copper, and an oxide of a metal' which is moreelectropositive than the metals of the aforementioned group.

The catalytic reduction or hydrogenation of organic compounds with aidof hydrogen is generally performed in presence of metallic catalysts,among which nickel, cobalt and copper have the premier place.Accordingly as the catal sis occurs in the gaseous phase or the liquiphase, the metal; its oxide or a' salt of it is used. When operating inthe liquid phase with the free metal as catalyst, the metal is generallyused in the form in which it is obtained by reducing its oxide or othercompound capable of reduction by means of hydro en. Obviously in suchcase the reduction 0% the oxide occurs at a high temperature.

For many catalytic purposes metallic catalysts thus made are notsufliciently active,

particularly at low temperatures which are necessary in many cases inwhich decomposition or secondary reaction would otherwise occur. I

We have now found that extraordinarily active catalysts are obtainablewhen the metal in question is separated directly from the aqueoussolution of its salt in the presence of a asic reacting compound such asammonia,

an organic base, an acidamide, etc., by means of a more electro-positivemetal. This separationpc'curs at a low temperature, which f .obviouslyis below the boiling point of. the

solution used. For example, nickel, cobalt or copper may easily beseparated from such solutions by means of iron, zinc or aluminium, avery finely subdivided metal being --obtained according to theconditions. 'It is advantageous to bring about this separation inpresence of a carrier, such as kieselguhr,

silica gel, carbon or the like, whereby increase of surface is obtained.When operating inthe manner described before there is obtained asby-p'roduct the oxide of the elec-' tro-positive-metalused for theseparation and PATENT, OFFICE CATALYSTS in the choice of this there is ameans of activating the catalyst. V

The catalysts obtainable in this manner are extraordinarily active. Theycan be used with particular advantage for-catalytic reduction orhydrogenation of organiccompounds, when carried out in the liquid phaseand at comparatively low temperatures. For example, aromatichydrocarbons or their derivatives, such as toluene or phenol, may beconverted into the corresponding hexa- -hydro-compounds even at atemperature of about 90-100 C; aliphatic compounds containing doublylinked carbon, as for instance cinnamic acid or certain fats, can beconverted into the saturated compounds at a temperature of about 80 O;aldehydes or "ke'tones may be converted into the corresponding alcoholsat a temperature of about 40450", C.;. quinones can be converted into.hydroquinones and nitriles into the corresponding amines at similartemperatures. So also nitro-, azoxy-,- azoor hydrazo-compounds can beconvertedinto the corresponding amines. In short, the catalysts have anextraordinarily varied application.

The following examples illustrate the invention, the parts being byweight Example 1.238 parts of crystallized nickel chloride are dissolvedin 1000 arts of water and mixed with 50 parts-o am.- monium chloride and700 parts of concentrated ammonia solution. To the solution thusobtained are added, while stirring, 300 parts of kieselguhr and thereare then introduced gradually at 8090 O. 100 parts of aluminium powder.When separation of nickel is finished the whole is stirred for. sometime; the catalyst consisting of metallic nickel, kieselguhr andaluminium oxide is separated from the liquid in the usual manner andthoroughly washed.

Example 2.238 arts of nickelous -chloride or a correspon mg quantity ofanother nickel salt are dissolved in 1000 parts of water and thesolution is mixed with 320 parts of pyridine. While stirring at 70 O.there are gradually added 180 parts of zinc dust and the mixture isgradually heated to 9095 C. When the separation of nickel KARL MARX,HEB-MANN BEHNCKE, AN D KARL BRODERSEN, OF DESSAU, GERMIANY, AS-

SIGNOBS TO I. G. FARBENINDUSTRIE AKTIENGESELLSCHAFT, OF FBANKFOBTFON-for one hour at 90-100 C The catalyst is then separated from the liquidand thorou hly washed.

' example '3.-280 parts of cobalt sulphate (COSO +7HO) are dissolved in1000 parts of Water'and the solution is mixed with 240 parts of urea.There are then added at 60-7 0 C. 110-120 parts of zinc dust,wherenesoyros ing of the organic bases, the acid amides, and. ammoma.

3. A catalyst comprising a metal of the group consisting of nickel,cobalt and copper and aluminium oxide, said catalyst being in a finelysubdivided state, forming amorphous flakes of gray to grayish-blackcolor and being capable of causing aromatic hydrocarbons to be convertedinto the corresponding hydro compounds when treated with upon the Wholeis stirred until separation o-.....hydiogen at a temperature of about100 C.

cobalt is at an end, the temperature being kept at 9095 C. Theprecipitate is filtered and washed until free from sulphate ions.

E mample 4.170 parts of crystallized cuprous chloride are dissolved in1000 parts of water, and the solution is mixed with 700 parts by volumeof concentrated ammonia solution. There are then added, while stirring,300 parts of kieselguhr and then at a temperature of about 7080 C. 100parts of aluminium powder. When the separation of copper is finished,the stirring is continued for some time before the reaction productconsisting of metallic copper, aluminium' oxide and kieselguhr isseparated from the reaction liquid and washed thoroughly.

What we claim is z- 1. l catalyst comprising a metal of the groupconsisting of nickel, cobalt and copper and an oxideof a metal which ismore electropositive than the metals of the aforementioned group, saidcatalyst being in a finely subdivided state, forming amorphous flakes ofgray to grayish-black color and being capable of causing aromatichydrocarbons to be a converted into the-corresponding hydro com- Isistmgof the organic bases, the acld amides,

pounds when treated with hydrogen at a temperature of about 100 C. andbeing obtainable-by causing an aqueous solution of a salt of one of thesaid metals to be reacted upon by a metal which is more electropositivethan the metals of the aforementioned group in the presence of-acompound of the group conand ammonia.

' '2. A catalyst comprising a metal of the group consisting of nickel,cobalt, and copper, an oxide oia metal which is more electropositivethan the metals of the aforementioned group, and a carrier, saidcatalyst being in a finely subdivided state, forming amorphous flakes ofgray to grayish-black color and being capable of causing aromatichydrocarbons to be converted into the corresponding hydro compounds whentreated with hydrogen at a temperature'of about 100 C. and beingobtainable by causing an aqueous solution of a salt of one of the saidmetals to be reacted upon by a metal which is more electropositive thanthe-metals of the aforementioned group in the presence-of a carrier anda compound of the group consistgroup consistin and being obtainable bycausing an aqueous solution of a salt of one of the said metals to bereacted upon by aluminium powder in the presence of a compound of thegroup consist ing of the organic bases, the acid amides, and

ammonia.

4. A catalyst comprising a metal of'the group consistin of nickel,cobalt and copper, aluminium oxi e, and a carrier, said catalyst beingin a finely subdivided state, .Vformmg amorphous flakes of gray tograyish-black color and being capable of causing aromatic hydrocarbonsto be converted into the corresponding hydro compounds when treated withhydrogen at a temperature of about 100 C. and being obtainable bycausing an aqueous solution of a salt of one of the said metals to bereacted upon by aluminium powder in the presence of a carrier and acompound of the group consisting of the organic bases, the acid amides,andalnmonia.

5. A catalyst comprising nickel and aluminium oxide, said catalyst beingin a finely subdivided state, formin amorphousflakes of gray tograyish-bloc color and being capable of causing aromatic hydrocarbons tobe converted into the corresponding hydro compounds when treated withhydrogen at a temperature of about 100 C. and being obtainable bycausing an aqueous solution of a nickel salt to be reacted upon byaluminium powder in the presence of a com ound of the of the orgamcbases, the acid amides, an ammonia.

6. A catalyst comprising nickel, aluminium oxide and a carrier, saidcatalyst being in a finel subdivided state,forming amor-. phous fla esof gra to grayish-black color and being capable of cau'sing aromatichydrocarbons to be converted into the corresponding hydro compounds whentreated with hydrogen at a temperature of about 100 C. and beingobtainable b causing an aqueous solution of a nickel sa t to be reactedupon aqueous solution of a salt of a'metal o the group consisting ofnickel, cobalt and copper to be reacted upon by a metal which is moreelectro-positive than the metals of the aforeamides, and

mentioned group, in the presence of a comound of the group consisting ofthe organic ases, the aci amides and 811111101118..

8. The process which comprises causing an aqueous solution of'a salt ofa metal of the group consisting of nickel, cobalt and copper tobereacted upon by aluminium powder,'in

. the presence of a compound of the group conacted upon by aluminiumpowder in the sisting of the organic bases, the acid amides and ammonia.

9. The process WhlCh comprlses causmg an aqueous solution of a nickelsalt to be reacted upon by a metal which is more electro-positive thannickel, in the presence of a compound of the group consisting of theorganic bases, the acid amides and ammonia. I

10. The process which comprises causing an aqueous solution of a nickelsalt to be represence of a compound of the group consisting oftheorganic bases, the acid amides and ammonia.

tures.

KARL MARX. HERMANN- BEHNCKE. KARL BRODERSEN.

In testimony whereof, we aflix our signa-

